JPS6017335B2 - Manufacturing method of silicone block polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel heat-curable silicone block polymer.

More specifically, number average molecular weight 9,000 to 10,00
0 methylpolysiloxane and C〆[(CH3)2Si○
] This invention relates to a method for producing a novel silicone block polymer synthesized from m(CH3)2SIC. Generally, silicone resins are obtained by co-hydrolyzing diorganodichlorosilane and monoorganotrichlorosilane.

Therefore, the obtained resin has diorganosiloxane units and monoorganosiloxane units randomly distributed. As the number of diorganosiloxane units increases, the final cured seaweed becomes more flexible, but its heat resistance deteriorates, and the resin before hardening is sticky and fluid, making it difficult to release hot water.
It is something. Conversely, as the number of monoorganosiloxane units increases, heat resistance increases, but the resin becomes brittle. Therefore, it has been difficult to obtain a resin with high heat resistance and flexibility using the above-mentioned hydrolysis method. Therefore, the present inventors have conducted extensive research to develop a silicone resin that satisfies the above requirements, that is, has high heat resistance and flexibility, and as a result, they have arrived at the present invention.

That is, the present invention has a number average molecular weight of 9.0 as shown below.
00 to 10,000 methylpolysiloxane in an organic solvent in the presence of an amine, 'B'C〆 [(C is) Bui○]
Provided is a method for producing a silicone block polymer, which is characterized by reacting m (C ratio) with iC〆 (in the formula, m = 0 to 100).

There are already known techniques for producing silicone block polymers from diorganosiloxane units and monoorganosiloxane units.

For example, in JP-A-49-93500, in a system consisting of water-acetone-water-immiscible organic solvent, the ratio between organic groups and Sj is determined by first hydrolyzing diorganodichlorosilane and then hydrolyzing monoorganochlorosilane. is 1
．． 4 to 1.7, the resulting polymers are flexible and can be dried to a non-tacky, non-flowing state before curing. It has been stated. The patent also states that if the hydrolysis reaction is carried out in the order of mo/organotrichlorosilane and then diorganodichlorosilane, the resulting resin is undesirably sticky. Furthermore, in U.S. Pat. No. 3,294,737, the following arylsilsesquioki (in the formula R=aryl group, 1=25-500) San and Y[R″2Si○]mR″2SjY (in the formula R″2
= alkyl group, aryl group, others, Y: halogen, hydroxyl group, m = 1 to 1000).

On the other hand, the manufacturing method of the silicone block polymer of the present invention is similar to the above-mentioned two known techniques, but
Methylpolysiloxane with a number average molecular weight of 9,000 to 10,000 shown below as a monoorganosiloxane unit■
Its characteristic lies in the use of .

That is, by using methylpolysiloxane (2), which has a relatively high molecular weight that has never been seen before, as a monoorganosiloxane unit and introducing diorganosiloxane units, the polymer targeted by the present invention can be obtained.

The polymer thus obtained has the characteristics of good adhesion and heat resistance, high scorching resistance, stripability of the cured product, and high mechanical strength, such as tensile strength. Methylpolysiloxane used in the present invention ■
For example, in Japanese Patent Application Laid-Open No. 53-88, which we filed earlier,
It can be manufactured by the manufacturing method disclosed in No. 09y. The manufacturing method is to dissolve methyltrichlorosilane (CH-3) in a mixed solvent of ketone and ether in the presence of an amine, dropwise add water to the solution, hydrolyze it, and heat condense.
In the present invention, methylpolysiloxane (2) having a number average molecular weight of 9,000 to 10,000 obtained by such a method is used. That is, in the present invention, the methylpolysiloxane (2) obtained as described above is treated with Cso[(CH3)2Si○]mSi(CH3) in an organic solvent in the presence of an amine.
) A block polymer is obtained by reacting with 2C.

The types of amines used here include almost all amines from primary to tertiary, but especially pyridine,
Triethylamine and the like are effective. Organic solvents include aromatic solvents such as benzene and toluene, dichloromethane,
Ha such as chloroform. It is possible to use alkanes, ethers such as diethyl ether and tetrahydrofuran, and ketones such as acetone and methyl isobutyl ketone, but in particular tetrahydrofuran (THF),
Methylsoptyl ketone and the like are effective.

C so[(CH3)2Si○]mSi(CH3)2C can be used from m=0 to 100, but especially when m=0 to 2
A high degree of yield gives favorable results. In terms of quantitative relationship, taking pyridine as an example, the amount of amine is preferably 0.1 to 1 part by weight per 1 part by weight of methylpolysiloxane.
Most preferably, it is about 0.5 part by weight. Taking tetrahydrofuran as an example, the amount of the solvent is preferably in the range of 3 to 1 part by weight, but about 5.5 parts by weight gives particularly preferable results.
C〆0 [(CH3)bui○]mSi(C ratio)2C evening is m
The optimum amount to add varies depending on the number of m, but if m=20 as an example, 0.1 to 0.5 parts by weight is preferable.

Among these, the most preferred is 0.2 to 0. It is about the same weight as Marugame. To describe the manufacturing procedure, methylpolysiloxane is dropped into a solvent, amine is added, and C〆[(CH3)2Si
0] Add mSi(CH3)2C and react.

The reaction temperature can be arbitrarily selected depending on the boiling point of the solvent, but the lower the temperature, the longer the reaction time needs to be. Preferably, the conditions are 50 qo and 2 hours. After the reaction is completed, the reactant is poured into methanol to obtain a polymer. In addition, C
(CH3)2Si○]mSi(CH3)2C It is also possible to obtain a block polymer by using diorganosiloxane having an amino group or alkoxy group instead of chlorine and reacting it with methylpolysiloxane. However, due to ease of manufacture, Cso[(CH3)2Si○]m
The method using Si(CH3)2C is most preferred.

The block polymer obtained in this way has a solid state measured in THF at 30°C, which is usually 0.1 to 0.
9 degrees Fahrenheit, and its structure is estimated to be as follows: When expressed as a methylpolysiloxane unit, that is, and as a diorganosiloxane unit, that is.

The block polymer obtained by the above production method has excellent adhesion to inorganic materials such as glass, silicon, aluminum, and metals, as well as excellent heat resistance and mechanical strength. By spin-coating the coating onto a glass or silicon substrate and then heating and curing it, a heat-resistant insulating film with a thickness of several m to several tens of mm can be obtained.

Furthermore, by mixing a curing catalyst with the block polymer of the present invention, a film that is flexible and has excellent heat resistance and mechanical strength can be obtained. Furthermore, it is possible to blend an inorganic filler or a heat-resistant pigment into the composition and use it as a molding or coating composition. Example 1 Methyl isobutyl ketone (65 cm) and tetrahydrofuran (23 cm) were placed in a reactor equipped with a reflux condenser, a dropping funnel, and a stirring bar, and methyl trichlorosilane (12 cm, 0.1 cm) was charged. mol), triethylamine (14', 0.1 mol) is added.

Cover the reaction vessel with ice and slowly add water dropwise while stirring. A white precipitate of triethylamine hydrochloride gradually forms, but it dissolves again by adding more water.
Next, the mixture is heated under reflux for 2 hours at a temperature of 100 to 110 qo using an oil bath. After the reaction is completed, the organic layer is separated, washed with water until the washing water becomes neutral, and dried over anhydrous sodium sulfate. Thereafter, the drying agent is removed, the mixture is concentrated to a point where the polymer precipitates, and the mixture is poured into methanol to precipitate the polymer. The obtained precipitate is thoroughly washed with methanol and dried under vacuum. The number average molecular weight of the produced methylpolysiloxane is approximately 9,000
It was hot. This polymer ([ri]=0.09, THF,
30℃) 4 females were dissolved in 225g of tetrahydrofuran,
After adding 20g of pyridine,
Add (CH3)2Si○]20Si(CH3)2C and react at 50°C for 2q hours. The reaction mixture is poured into methanol to precipitate the block polymer. The obtained polymer is thoroughly washed with methanol and then vacuum dried. The yield of flock polymer is 41g, and the intrinsic viscosity is 0.4.
5 (THF, 3000). This block polymer material was dissolved in toluene 4', molded on a polyfluoroethylene plate, and then heated and cured at 150 qo for 2 hours. When calorimetric analysis (heating rate: 15 qo/min) was performed, weight loss started. The temperature is 250 o'clock and 700 o'clock
The weight residual rate at q0 was 83%, indicating high heat resistance. Usage Example 1 100 parts by weight of the block polymer obtained in Example 1 was dissolved in 280 parts by weight of toluene, and 0.0% of triethanolamine was added as a curing catalyst. A portion by weight of the box was added, and a heat-cleaned glass cloth was impregnated with this, and the toluene was removed by hot air drying to obtain a molding material.

Next, the molding material obtained above was layered for 19 minutes, and the molding temperature was 16 degrees.
After lamination molding was carried out for 19 minutes at 0° C. and a molding pressure of 100 k9/m, the mold was dismantled to obtain a molded product. This product had no bulges or layer divisions, and had the following excellent physical properties. Bending strength: 14k9/block Breakdown voltage: 1
Fox V/skin heat resistance: 30,000, no changes such as layer splitting or blistering after heating for 3 hours.

Comparative Example 1 Commercially available silicone resin (manufactured by Toray Silicone, SH
840), and a molded article was obtained in the same manner as described in Use Example 1.

Its physical properties were as follows. Bending strength: 8-12
k9/Dielectric breakdown voltage: 10-14 KV/Yanagi Heat resistance: After heating at 300 oo for 3 hours, swelling and layer cracking were observed in some parts.

Use Example 2 The block polymer obtained in Example 1 was dissolved in xylene (solid content concentration 34%, viscosity 4 ps).

Spread this solution on a silicon wafer 500 times. p. m. After spinning for 30 seconds, apply 1. with 300qo. A coating film of 2 to 3 meters was obtained by heating and curing between insect cages. This product also did not peel off in the cross-cut test after heating at 450 oo for 1 hour. Explanation of the cross-cut test; Use a knife to make cross-cut lines on the coating surface at intervals of one skin in the vertical and horizontal directions, apply sellotape to this, peel it off, and show the survival rate of the squares remaining on the board. .

If the adhesion is excellent, no peeling will be observed. When peeled off, the large number of remaining particles generally corresponds to good adhesion.
Usage example 3 After dissolving the block polymer obtained in Example 1 in 5' of toluene, glass, aluminum, stainless steel, and copper (metals are polished with sandpaper, treated with ultrasonic waves, washed with a solvent, and dried) (used) and air-dried at room temperature.

After air drying, heat curing was performed at 200 qo for 2 hours. When the coating film obtained in this way was subjected to a cross-cut test, the residual rate was 100% on glass and aluminum, and on stainless steel,
Copper showed a survival rate of over 90%. Usage Example 4 The block polymer obtained in Example 1 was mixed with toluene6. Already dissolved.

Apply this solution to aluminum paste [Manufactured by Tokai Kinzoku ■, Altop #13] 1. Gradually add it to the group to make an aluminum dispersion. Add to this 0.0 tin octylate as a curing catalyst.
The mixture was applied to a steel plate that had been previously treated with sandpaper, and sanded at 150°C for 30 minutes. The resulting coating film (approximately 10 layers thick) was tested for adhesion and heat resistance. The results are shown in the table below. Comparative example 2
Commercially available silicone resin (manufactured by Toray Silicone, SH
840) with the same formulation as in Use Example 4, applied under the same conditions as in Use Example 4, and after dawning, the performance of the paint film was tested.

The results are also shown in the table above. Usage Example 5 A 40% toluene solution of the block polymer obtained in Example 1 was prepared, 0.002 parts by weight of dibutyltin dilaurate was added as a curing catalyst per 1 part by weight of the polymer, and the mixture was mixed with polyfluorinated ethylene Sakagami. Cast with
After leaving it at room temperature to allow most of the solvent to evaporate,
It was heated and cured for 2 hours.

After curing, the film was peeled off from the polyfluoroethylene plate and subjected to a tensile test, and as a result, the tensile strength was 75k9/m. Comparative Example 3 Commercially available silicone resin (manufactured by Toray Shi IJ Corn ■, S
A casting film was prepared using H840) and a curing catalyst (tin octylate), and a tensile test was conducted after curing. As a result, the tensile strength was 50k9/m.

Claims (1)

[Scope of Claims] 1 (A) A number average molecular weight of 9,000 to 10 as shown below,
000 Methylpolysiloxane▲Mathematical formulas, chemical formulas, tables, etc.▼ In the presence of an amine, in an organic solvent (B)Cl[(CH_3)_2SiO]m(CH_3)
A method for producing a silicone block polymer, which comprises reacting with _2SiCl (in the formula, m=0 to 100).